EP0678782A1 - Méthode de fabrication de composition solide pour le traitement de matériaux photographiques à l'halogénure d'argent sensibles à la lumière - Google Patents

Méthode de fabrication de composition solide pour le traitement de matériaux photographiques à l'halogénure d'argent sensibles à la lumière Download PDF

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Publication number
EP0678782A1
EP0678782A1 EP95302458A EP95302458A EP0678782A1 EP 0678782 A1 EP0678782 A1 EP 0678782A1 EP 95302458 A EP95302458 A EP 95302458A EP 95302458 A EP95302458 A EP 95302458A EP 0678782 A1 EP0678782 A1 EP 0678782A1
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Prior art keywords
group
granules
procedure
samples
dressing
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German (de)
English (en)
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EP0678782B1 (fr
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Takashi c/o Konica Corp. Deguchi
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Konica Minolta Inc
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Konica Minolta Inc
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/20—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by expressing the material, e.g. through sieves and fragmenting the extruded length

Definitions

  • the invention relates to a solid developing composition in the form of powder, granules or tablets for a silver halide photographic light-sensitive material.
  • a silver halide photographic light-sensitive material is usually processed using a color developer, a bleach, a bleach-fixer, a fixer and a stabilizer to obtain an imagewise image.
  • the components of the processing solutions used herein are packaged in plastic bottles for easy use in the form of one or more concentrated solutions and are supplied as a processing solution kit to consumers. The consumers dilute the component solutions of the kit with water to prepare the processing solutions (as starter solutions or replenisher solutions) and use them.
  • mini-labs which process a photographic material using a small automatic processor
  • the processing kit in concentrated solution form still requires much storage space. Further, the cost for transport is not low.
  • the discarded plastic bottles increase year by year and should be recovered, however the recovering is difficult and therefore, development of a processing system in which waste plastics are reduced is demanded.
  • Powder photographic processing agents are considered in order to reduce storage space, transport cost and the amount of the plastic waste.
  • the powder agents produce loose powder when it is dissolved in water, and operators breathe in loose powder particles, resulting in health hazard.
  • the present inventor has found that other photographic solutions may be contaminated with the components of the loose powder and there occurs the possibility of other trouble in developing process.
  • Japanese Patent O.P.I Publication Nos. 5-119454/1993, 5-119450/1993 and 5-142708/1993 disclose granulated solid processing composition.
  • Japanese Patent O.P.I. Publication No. 5-224361/1993 discloses granules obtained in a dry granulator and tablets obtained by compression molding.
  • the solid processing agent produced by this method is effective for a uniform mixture of components in small amounts, however, the granule strength is not sufficient, since water or an aqueous solution is not used as a binder and has a defect that fine powder occurs due to vibration after storage.
  • Japanese Patent O.P.I. Publication No. 5-197090/1993 discloses tablets having a of 25 to 50% produced by compression molding granules obtained in a stirring granulator.
  • the solid processing agent produced by this method is effective for prevention of insoluble matter occurrence and shortage of dissolving time and its strength is sufficient, however, the control of the grain size is difficult. It has been found that the granules have a defect that there occurs fluctuation of a supplying amount, since the granule size is not sieved and small or large granules are present in admixture.
  • Japanese Patent O.P.I. Publication Nos. 2-109042/1990 and 4-221951/1992 disclose a solid processing agent obtained in a fluid bed granulating dryer which reduces dust occurrence.
  • the solid processing agent produced by this method is effective for prevention of fine powder immediately after the manufacture and has a predetermined particle size, however, it has been fount that the granules have a defect that fine powder occurs due to vibration after storage, since the strength is not sufficient.
  • a first object of the invention is to provide a method of manufacturing a solid developing composition for a silver halide color photographic light-sensitive material reducing fine powder occurrence due to vibration after storage.
  • a second object of the invention is to provide a method of manufacturing a solid developing composition for a silver halide color photographic light-sensitive material capable of reducing fluctuation of a supplying amount.
  • Fig. 1 shows temperature conditions in a thermostatted chamber.
  • Fig. 2 shows a plan view and a side view of a tablet supplying means.
  • the inventors have found the followings by experiments regarding a manufacturing method of a solidified developing processing composition for a silver halide photographic light-sensitive material.
  • the solid processing granules containing additives within a limited range prepared in a stirring granulator are those having a high density, and are superior in granule strength and prevention of fine powder occurrence after storage to those prepared in a fluid bed granulator.
  • supplying of granules refers to supplying granules to, for example, receivers for compression-molding into tablets, packages or processing tanks.
  • a method for manufacturing a solid developing composition for a silver halide color photographic light-sensitive material can be provided, which reduces fine powder occurrence due to vibration after storage and reduces fluctuation of a supplying amount, the method comprising dressing granules obtained by granulating with stirring.
  • Dressing granules in the invention means a process for obtaining granules having not more than the desired granule size from granules having not less than the desired granule size crushing granules having about 2000 ⁇ m or more to less granule size, for example, with a breaking feather.
  • the dressing is different from pulverization before granulating to not more than 100 ⁇ m.
  • Simply sieving does not comprise crushing granules to less particle size and therefore, is different from the dressing.
  • components in small amounts are incorporated in large particles, resulting in fluctuation of the supplying amount. Therefore, the classifying is also different from the dressing of the invention.
  • granules may be dressed directly in a dressing apparatus, and may be dressed after sieving with a specific screen in order to prevent fine powder occurrence, however, granules are preferably dressed directly in a dressing apparatus in view of productivity.
  • the invention encompasses dressing a part of granules during drying.
  • a hammer mill, roll mill or screen mill method can be used as a dressing method.
  • apparatuses available on the market such as Comminutor (produced by Fuji Powder Co., Ltd.), OG-1 (produced by Kikusui Seisakusho Co., Ltd.) and New Speed Mill (produced by Okada Seiko Co., Ltd.).
  • dressing may be carried out after granulating, but is preferably carried out during drying in view of effective drying or moisture absorption of granules, and more preferably during and after drying in granules easily subjected to blocking.
  • the dressing during drying refers to dressing during a period from the beginning of drying until the end of drying.
  • moisture content of granules is not more than 4 wt% and more preferably when not more than 3 wt%.
  • the moisture content referred to herein is a weight reduced when granules are dried at 90°C for 10 minutes in an electric moisture meter available on the market and is represented by weight percentage (%).
  • the particle diameter of granules are preferably controlled using a screen in view of quantitative supply and miscibility with other granules.
  • the screen used during dressing preferably has 0.5 to 3.0 mm mesh, and more preferably 0.5 to 2.0 mm mesh.
  • the granules after dressing preferably have 70 wt% or more of granules having a particle diameter of 149 to 2000 ⁇ m in view of quantitative supply and granule hardness in compression-molding, and more preferably have 70 wt% or more of granules having a particle diameter of 149 to 1490 ⁇ m.
  • the drying method includes a fluid bed method, a box method, an air drying method, a vacuum method or a freeze-dry method.
  • the drying method is preferably a fluid bed method in view of drying efficiency and granule strength.
  • the drying temperature is preferably 80°C or less in a fluid bed method.
  • the drying temperature is especially preferably 65°C or less in view of granule strength in manufacture.
  • the drying end in the invention is when the moisture content of granules is 2 wt% or less after granules were dried at 90°C for 10 minutes in an electric moisture meter available on the market.
  • the granules of the invention refers to as granules granulated to have an average particle diameter of 150 to 3000 ⁇ m.
  • the meshes of the screens used herein are 3360, 2830, 2000, 1410, 1000, 710, 500, 350, 210, 149, 105 and 37 ⁇ m.
  • the granulating of the invention refers to granulating using a liquid such as water, an aqueous solution, methanol, ethanol or a mixture thereof as a binder. Water or an aqueous solution is preferably used in view of prevention of explosion and safety of operation.
  • the granulating with stirring in the presence of a liquid of the invention refers to as preparing aggregated particles of powder by stirring fine powder while adding an appropriate liquid binder and excludes granulating in a fluid bed or in a dryer.
  • the granulating time refers to time taken from the beginning of water addition until the end of stirring.
  • Granulation is preferably carried out, in view of drying property and prevention of aggregation among granules, not to exceed 10 wt% of a liquid binder based on the weight of the composition to be granulated. "Not to exceed 10 wt%" refers to "not to exceed 10 wt% in the end of granulation, although the binder may exceed 10 wt% temporarily during granulation".
  • Tablets obtained by compression-molding into tablets the solid processing composition prepared by the above method exhibit the effects of the invention markedly, effectively prevent fine powder occurrence due to vibration after storage, and have sufficient strength.
  • the compression pressure is 400 to 2000kg/cm2
  • the invention is effected more markedly.
  • Tablets obtained by tableting a mixture of the granules of the invention is also effected more markedly.
  • the solid processing tablet is produced by well known compressors.
  • the compressors for producing the tablets include a hydraulic press machine, a single tableting machine, a rotary tableting machine and a bricketing machine can be used.
  • the solid processing tablet may be in any form, but is preferably in the cylindrical or parallelepiped form in view of producibility or processability, and more preferably in the cylindrical form.
  • the tablets preferably have chamferings without corners in view of prevention of defects in processing or coating.
  • lubricants or other additives may be added for facilitating tableting or for other objects.
  • Hardness in the invention refers to compressive breaking strength, and, in the solid processing tablet, refers to strength in a perpendicular direction to a tableting direction on tableting and in a direction to give a maximum distance in a compression direction.
  • Hardness can be measured by means of an apparatus available on the market such as a Monsant hardness meter, a Stoke hardness meter or Speed Checker (produced by Okada Seiko Co., Ltd.).
  • Granular strength can be measured by means of an apparatus available on the market such as Grano produced by Okada Seiko Co., Ltd..
  • the method of the invention comprises a process for granulating with stirring in the presence of a liquid at least one component, particularly, a photographic processing agent, contained in the granular solid processing composition of the invention for a silver halide photographic light-sensitive material.
  • the photographic processing agent of the invention refers to a pH adjusting agent, a preservative, a developing agent, a bleaching agent, a fixing agent, a rehalogenating agent or a chelating agent, which is a material essential for a stable and sufficient photographic processing.
  • the alkali agent of the invention is a compound giving pH 8 or more in its aqueous solution.
  • the preferable example includes sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium hydroxide, potassium hydroxide and lithium hydroxide.
  • Sodium carbonate, sodium bicarbonate, sodium borate and trisodium phosphate are preferable in view of moisture prevention. In the invention sodium carbonate is especislly preferable.
  • the p-phenylene diamine type compound used in the invention will be explained below.
  • the p-phenylene diamine type compound includes a compound represented by the following Formula [I], [II] or [III].
  • R1 and R3 may be the same or different, and independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group or a hydroxyethyl group; and R2 represents a hydroxyethyl group, a methoxyethyl group, a sulfoalkyl group, a carboxyalkyl group or a ⁇ -methanesulfonamido group,
  • R4 and R5 independently represent an alkyl group having 1 to 4 carbon atoms; and R6 represents a straight-chained or branched alkylene group having 3 to 4 carbon atoms,
  • R7 represents an alkyl group
  • R8 represents an alkylene group having two or more carbon atoms
  • R9 and R10 may be the same or different and independently represent a hydrogen atom or an alkyl group having not more than 4 carbon atoms
  • R11 represents a substituent
  • n is an integer of 0 to 4, provided that when n is 2 or more, R11 may be the same or differen.
  • the above p-phenylene diamine compound having at least one hydrophilic group which is positioned on the amino group or benzene nucleus is preferably used in view of no stains on a light sensitive material and less stimulation on skin.
  • the typical hydrophilic group preferably includes -(CH2) n -CH2OH, -(CH2)-NHSO2-(CH2) n -CH3, -(CH2) m -O-(CH2) n -CH3, -(CH2CH2O) n C m H2 m+1 , -(CH2) m -CON(C m H 2m+1 )2, (in which m and n are each an integer of not less than 0), -COOH group and -SO3H group.
  • the hydroxylamine derivative includes a compound represented by the following Formula [IV] wherein R12 and R13 independently represent a hydrogen atom, a substituted or unsubstituted alkyl, aryl or heterocyclic group or R14CO- wherein R14 represents an alkyl group, an alkoxy group, an aryl group or an amino group, provided that R12 and R13 may combine to form a nitrogen containing heterocyclic ring.
  • the substituted alkyl group of R12 and R13 is preferably a substituted alkyl group having 1 to 3 cabon atoms, and may be the same or different.
  • the substituent of the alkyl group includes a hydroxy group, a sulfo group, a phosphonic acid group, an alkoxy group, a carbamoyl group and a cyano group.
  • Compounds IV-12 through IV-20 and IV-27 can be used in the form of an alkali metal salt (sodium, potassium or lithium salt).
  • Fomula [IV] are usually used in free amine or in the form of hydrochloric acid, sulfate, p-toluenesulfonic acid, oxalic acid, phosphoric acid or acetic acid salt.
  • the compounds represented by Fomula [IV] are preferably solids in view of the objects of the invention. Of these the especially preferable are the compounds given below.
  • ferric complex of an amino polycarboxylic acid in the invention will be explained below.
  • the ferric complex of an amino polycarboxylic acid refers to a ferric complex of the following free acid represented by the following Formula [V] wherein T1 represents a hydrogen atom, a hydroxy group, a carboxy group, a sulfo group, a carbamoyl group, a phosphono group, a phosphon group, a sulfamoyl group, a substituted or unsubstituted alkyl group, an alkoxy group, an alkylsulfonamido group, an alkylthio group, an acylamino group or a hydroxamic acid group, a hydroxyalkyl group or wherein W1 represents a substituted or unsubstituted alkylene, arylene, alkenylene, cycloalkylene or aralkylene group or wherein X represents -O-, -S-, a divalent heterocyclic group or
  • R15 through R19 independently represent a hydrogen atom, a hydroxy group, a carboxy group, a sulfo group, a carbamoyl group, a phosphono group, a phosphon group, a sulfamoyl group, a sulfonamido group, an acylamino group or a hydroxamic acid group, provided that at least one of R15 through R19 is a carboxy group.
  • L1 through L7 independently represent a substituted or unsubstituted alkylene, arylene, alkenylene, cycloalkylene or aralkylene group; and l1 through l7 independently represent an integer of 0 to 6, provided that l1 through l7 are not simultaneously 0.
  • amino polycarboxylic acid represented by Formula [V] constituting the ferric complex of an amino polycarboxylic acid will be shown below.
  • V-1) through (V-8), (V-12), (V-14) through (V-20), (V-22), (V-23) and (V-27) are preferable, and (V-1), (V-2), (V-6), (V-12), (V-14), (V-15) and (V-17) are especially preferable.
  • the content ratio of a Fe3+ ion to an amino polycarboxylic acid is preferably 1:1, and in (V-9) or (V-15) the ratio is preferably 1:2.
  • the salt of the ferric complex of an amino polycarboxylic acid may have an ammonium, potassium, sodium or hydrogen ion as a pair ion.
  • a thiosulfate used in the invention will be explained below.
  • the thiosulfate are preferably used sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate in view of photographic properties, and sodium thiosulfate or potassium thiosulfate is especially preferable.
  • the solid processig composition in the invention includes a compound represented by the following Formula [A], in view of prevention of fine powder occurrence.
  • the n1 valent organic group represented by A includes an alkylene group (such as methylene, ethylene, trimethylene or tetramethylene), an alkenylene group (such as ethenylene), an alkinylene group (such as ethynylene), a cycloalkylene group (such as 1,4-cyclohexanediyl), an arylene group (such as o-phenylene group or p-phenylene), an alkanetriyl group (such as 1,2,3-propanetriyl) or an arylenetriyl group (such as 1,2,4-benzenetriyl).
  • alkylene group such as methylene, ethylene, trimethylene or tetramethylene
  • an alkenylene group such as ethenylene
  • an alkinylene group such as ethynylene
  • a cycloalkylene group such as 1,4-cyclohexanediyl
  • an arylene group
  • the above n valent organic group includes a group having a substituent (such as a hydroxy group, an alkyl group or a halogen atom).
  • a substituent such as a hydroxy group, an alkyl group or a halogen atom.
  • the examples include 1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene or chloroethenylene.
  • the preferable compound represented by Formula [A] will be shown below.
  • the salt of the above acid includes an ammonium salt, a lithium salt, a sodium salt or a potassium salt, and the sodium salt or potassium salt is preferable in view of storage stability.
  • These organic acids or salts thereof may be used singly or in combination.
  • granules of the complex may be mixed with granules of the organic acid and/or the salt.
  • granules of a mixture of the complex with the organic acid and/or the salt displays the effects of the invention more markedly. Further, the mixture, compression-molded into tablets, gives tablets excellent in the strength.
  • the solid processing composition of the invention preferably contains a sulfite, a bisulfite, a metabisulfite, a bisulfite adduct or a hydroxylamine derivative.
  • a solid processing composition comprising an alkali agent
  • moisture absorption during storage is reduced, and surprisingly expansion due to moisture absorption is greatly reduced.
  • a solid processing composition comprising a thiosulfate
  • storage stability during drying is greatly improved, which enables the drying temperature to elevate, resulting in shortening drying time and improving productivity.
  • the bisulfite adduct includes compounds represented by the following Formula [G] or [G']:
  • R29 represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, a carboxyl group, a benzoyl group, an acyl group, a formyl group or a carbamoyl group, each being substituted or un substituted; and R30 represents a hydrogen atom or a methyl group,
  • Y represents an atomic group necessary to form a 3 through 6-membered cycloalkyl group or a heterocyclic ring; and Z represents a substituent; and n is an integer of 0 to 5, provided that when n is 2 to 5, Z may be the same of different.
  • the solid processing composition of the invention may contain a halide.
  • the halide includes sodium chloride potassiun chloride, ammonium chloride, potassiun bromide, sodium bromide, ammonium bromide, potassiun iodide, sodium iodide or ammonium iodide.
  • sodium chloride potassiun chloride ammonium chloride, potassiun bromide, sodium bromide, ammonium bromide is preferably used and surprisingly has the effect of preventing fine powder occurrence due to vibration during storage.
  • the solid processing composition may further contain a compound represented by the Following Formula [E]: wherein X1, X2, Y1 and Y2 independently represent a hydroxy group, a halogen atom, a morpholino group, an alkoxy group, an aryloxy group, analkyl group, an aryl group, an amino group, an alkylamino group or an arylamino group; and M represents a hydrogen atom, an alkali atom or other cations.
  • Formula [E] wherein X1, X2, Y1 and Y2 independently represent a hydroxy group, a halogen atom, a morpholino group, an alkoxy group, an aryloxy group, analkyl group, an aryl group, an amino group, an alkylamino group or an arylamino group; and M represents a hydrogen atom, an alkali atom or other cations.
  • the alkoxy group represented by X1, X2, Y1 or Y2 includes methoxy, ethoxy or methoxyethoxy;
  • the aryloxy group includes phenoxy or p-sulfophenoxy;
  • the alkyl group includes methyl or ethyl;
  • the aryl group includes phenyl or methoxyphenyl;
  • the alkylamino group includes methylamino, ethylamino; propylamino, dimethylamino, cyclohexylamino, ⁇ -hydroxyethylamino, ⁇ -dihydroxyethyamino, ⁇ -sulfoethylamino,N- ⁇ -sulfoethyl-N'-methylamino or N- ⁇ -hdroxyethyl-N'-methylamino;
  • the arylamino group includes anilino, o-, m
  • the above compounds can be prepared by a conventional method.
  • E-4, E-24, E-34, E-35, E-36, E-37, E-41 and E-44 are especially preferable.
  • the content of these compounds in granules is preferably 0.1 to 50 wt%, and more preferably 1 to 30 wt%.
  • the solid processing composition preferably contains compounds represented by the Following Formulas [VI] through [IX]: This is because reaction by air or heat during granulating or drying can be prevented even when water having a high concentration of metal ion (an iron ion or a carcium ion) used.
  • R20 represents a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms; and R21, R22 and R23 independently represent a hydrogen atom, a halogen atom, a sulfonic acid group or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms,
  • the compounds of Formula [VI] include 1,2-dihydroxyethyl-1,1-diphosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid or 1-hydroxypropylidene-1,1-diphosphonic acid, and one or two or more of these may be used.
  • 1-Hydroxyethylidene-1,1-diphosphonic acid is especially preferable in the invention, and may be used in the form of an alkali metal salt such as a sodium, potassium or lithium salt.
  • a sodium salt is preferable, and a tri- or tetra sodium salt is especially preferable.
  • the compounds of Formula [VII] include 1,2-dihydroxybenzene, 4-propyl-1,2-dihydroxybenzene, 1,2-dihydroxybenzene-3,5-disulfonic acid, 1,2-dihydroxybenzene-3,5,6-trisulfonic acid, 1,2,3-trihydroxybenzene, 1,2,3-trihydroxybenzene-5-carboxymethylester, 1,2,3-trihydroxybenzene-5-carboxy-n-butylester or 5-t-butyl-1,2,3-trihydroxybenzene, and one or two or more of these may be used.
  • 1,2-dihydroxybenzene-3,5-disulfonic acid or 1,2-dihydroxybenzene-3,5,6-trisulfonic acid is especially preferable in the invention, and may be used in the form of an alkali metal salt such as a sodium or potassium salt.
  • a sodium salt is preferable.
  • the salt may be an anhydiride or a hydrate.
  • R24 represents a hydroxyalkyl group having 2 to 6 carbon atoms
  • R25 and R26 independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 2 to 6 carbon atoms, benzyl group or -C n H 2n -N(X) (Y), wherein n is an integer of 1 to 6 and X and Y independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms.
  • These compounds may be used in the form of a free amine or a salt with hydrocloric acid or surfuric acid. These compounds may be used singly or in combination of two or more kinds.
  • R28-(O) n SO3X5 wherein R28 represents an alkyl group having 1-8 carbon atoms or a phenyl group
  • a substituted of unsubstituted alkyl group having 1 to 8 carbon atoms represented by R28 includes for example, a methyl group, a carboxymethyl group, a phenylmethyl group, an ethyl group, a hydroxyethyl group, a sulfonylethyl group, a propyl group, a butyl group, a tert-butyl group, a heptyl group, an iso-octyl group or a furanyl group.
  • These groups may be straight-chained or branched and may also include those each having a substituent.
  • Such substituents include, for example, a halogen atom (such as a chlorine atom or a bromine atom), an aryl group (such as a phenyl group), a hydroxyl group, an amino group, a nitro group, a carboxylic acid group (including the salts thereof) and a sulfonic acid group (including the salts thereof).
  • a halogen atom such as a chlorine atom or a bromine atom
  • an aryl group such as a phenyl group
  • a hydroxyl group such as an amino group, a nitro group, a carboxylic acid group (including the salts thereof) and a sulfonic acid group (including the salts thereof).
  • the phenyl group represented by R28 includes those each having a substituent.
  • substituent includes, for example, a halogen atom (such as a chlorine atom and a bromine atom), an alkyl group (including, preferably, an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an iso- propyl group or a butyl group), a hydroxyl group, an amino group, a nitro group, a carboxylic acid group (including the salts thereof) and a sulfonic acid group (including the salts thereof).
  • the substituent on the phenyl group may be a single substituent or 2 to 5 substituents. In the case of 2 to 5 substituents, these substituents may be the same as or the different from each other.
  • R28 may represent a polymer chain having a repetition unit derived from an ethylenically-unsaturated group.
  • R28 represents, preferably, a phenyl group and, preferably, a phenyl group having a substituent.
  • the preferable substituents thereto include, for example, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group, a carboxylic acid group (including the salts thereof) and a sulfinic acid group (including the salts thereof).
  • X5 represents a hydrogen atom, an alkali metal atom or an ammonium group, and the alkali metal atom include a sodium atom, a potassium atom or a lithium atom.
  • X5 preferably represents a sodium atom, a potassium atom or an ammonium group, and n preferably is 0.
  • each of compounds having a sulfonic acid group or a carboxyl group include its salts such as sodium, potassium, lithium and ammonium.
  • the solid processing composition of the invention may contains a compound represented by the following Formula [H] or [J].
  • the addition of the compound represented by the following Formula [H] or [J] eliminates an addiyion of an aldehyde which causes a sulfide precipitation.
  • Z represents an atomic group necessary to form a hydrocarbon ring or a heterocyclic ring
  • X represents an aldehyde group, wherein R1 and R2 independently represent a lower alkyl group and n is an integer of 1 to 4.
  • Z represents an atomic group necessary to form a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocyclic ring, provided that the ring may be a single or condensed ring.
  • Z preferably represents an aromatic hydrocarbon ring or a heterocyclic ring, each having a substituent.
  • the substituent includes an aldehyde group, a hydroxy group, an alkyl group, an ether group, a halogen group or a characteristic group.
  • the hydrocarbon ring of Z preferably is a benzene ring
  • the heterocyclic ring of Z preferably is a 5- or 6-membered heterocyclic ring or or a condensed ring.
  • the compounds represented by Formula [H] include compounds (1) through (90) described in US Patent No. 5,278,033.
  • Compound (H-2) is most preferable of compounds represented by Formula [H].
  • R1 and R2 may be the same or different and independently represent a hydrogen atom or a substituent, provided that R1 and R2 may combine each other to form a ring.
  • the substituent represented by R1 and R2 is not limited, but is preferably a hydrocarbon group, a characteristic group, a halogenated hydrocarbon group, an acyl group, a heterocyclic group or an ether group.
  • the group represented by R1 and R2 further has a substituent, and the substituent is preferably a hydroxy group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, an acid group or an alkoxy group.
  • the compounds represented by Formula [J] include compounds (A-1) through (A-76) described on pages 10-20 in Japanese Patent O.P.I. Publication No. 4-359249/1992 or compounds (X-1) through (X-76) described on pages 14-23 in Japanese Patent O.P.I. Publication No. 4-362943/1992.
  • Compound (J-3), (J-5) or (J-6) is most preferable of compounds represented by Formula [J].
  • Compounds represented by Formula [J] are preferably used in combination with a nitrogen-containing heterocyclic compound.
  • the nitrogen-containing heterocyclic compound includes 1,2,4-triazole or imidazole and further compounds (I-1) through (I-48) described on pages 4-7 in Japanese Patent O.P.I. Publication No. 4-359249/1992.
  • the invention is further effected in view of strength of granules.
  • the saccharide and /or water soluble polymer may be used during granulating as a solid mixture with a carbonate, a solution or in combination of a solid and a solution.
  • the preferable compound will be shown below, but the invention is not limited thereto.
  • a water soluble polymer includes polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl acetal, polyvinyl acetate, an aminoalkylmethacrylate copolymer, methacrylic acid-methacrylate copolymer, methacrylic acid-acrylate copolymer, and methacrylic acid betaine type polymer.
  • a saccharide includes a monosaccharide such as glucose or galactose, disaccharide such as maltose, sucrose or lactose, a sugar alcohol such as mannitol, sorbitol or erythritol, pullulan, methylcellulose, ethylcellulose, hydroxypropyl-cellulose, hydroxypropylmethylcellulose, cellulose acetate phthalate, hydroxypropylmethylcellulose phthalate, hydroxypropylmethylcellulose acetate succinate, dextrin or starch dissociate.
  • a monosaccharide such as glucose or galactose
  • disaccharide such as maltose, sucrose or lactose
  • a sugar alcohol such as mannitol, sorbitol or erythritol
  • pullulan methylcellulose, ethylcellulose, hydroxypropyl-cellulose, hydroxypropylmethylcellulose, cellulose acetate phthalate, hydroxypropylmethyl
  • the preferable are a block polymer of polyethylene glycol and polypropylene glycol, polyethylene glycol (weight average molecular weight of 2,000 to 20,000), a methacrylic acid-methacrylate copolymer or methacrylic acid-acrylate copolymer reperesented by Oidragid produced by Rehm Pharma Co., erythritol, maltose, mannitol, dextrin or starch dissociate represented by Pineflow and Pinedex produced by Matsutani Kagaku Co., Ltd., and methacrylic acid betaine type polymer represented by Yuka Former produced by Mitsubishi Yuka Co., Ltd.
  • the content of these compounds is preferably 0.5 to 20% by weight and especially preferably 0.5 to 20% by weight based on the weight of the solid processing composition.
  • Example 2 In the same manner as in Example 1, the above compound was pulverized at 30°C and not more than 50%RH to have a particle size of not more than 100 ⁇ m.
  • the resulting powder was granulated with stirring in the presence of a liquid in a NEW SPEED KNEADER (produced by Okada Seiko Co., Ltd.) by spraying 1000ml of water as a binder at a rate of 750ml/min.
  • a NEW SPEED KNEADER produced by Okada Seiko Co., Ltd.
  • sample (1-2) was obtained.
  • sample (1-4) was obtained.
  • Procedure (1-5) The compounds of Procedure (1-5) were pulverized, granulated, dried and dressed in the same manner as in Procedure (1-5) to obtain granules having a moisture content of not more than 2 wt%. The resulting granules were dressed one more time in the same manner as in Procedure (1-3). Thus, sample (1-7) was obtained.
  • Procedure (1-7) The compounds in Procedure (1-7) were pulverized, granulated, dried and dressed in the same manner as in Procedure (1-5) to obtain sample (1-9).
  • Procedure (1-7) The compounds in Procedure (1-7) were pulverized, granulated, dried and dressed during and after drying in the same manner as in Procedure (1-6) to obtain sample (1-10).
  • Procedure (1-9) was carried out to obtain sample (1-11), except that potassium carbonate 1.5 hydrate was used instead of anhydrous potassium carbonate.
  • Procedure (1-9) was carried out to obtain sample (1-12), except that potassium carbonate monohydrate was used instead of anhydrous potassium carbonate.
  • the sealed packages were stored for 2 weeks in a thermostatted chamber in which the temperature varied as shown in Fig. 1, and thereafter, subjected to a vibration test under the following condition using a vibration tester BF-UA produced by IDEX Co., Ltd.
  • the resulting samples were sieved with a 105 ⁇ m sieve, and evaluated for fine powder occurrence. The samples less than 105 were evaluated as fine powder. The results are shown in Table 1.
  • the vibration was carried out for 30 minutes under condition of 5-67Hz/210sec.
  • the evaluation criteria are as follows:
  • the evaluation criteria are as follows.
  • the evaluation criteria are follows:
  • the samples of ⁇ have adverse affect on processing properties in continuously processing.
  • the above compounds were pulverized in the same manner as in Procedure (1-2).
  • the resulting powder was mixed in a stirring granulator for 4 minutes and granulated for 3 minutes by adding water at a rate of 750 ml/min. in an amount shown in Table 3 (based on the total weight of the above compounds).
  • the resulting granules were dried in a fluid bed drier in the same manner as in Procedure (1-2).
  • the dressing was carried during and after drying using a 1.0 mm screen. Thus, samples (3-1) through (3-7) were obtained.
  • Samples prepared in Examples 1, 2 and 3 (shown in Tables 4 and 5) were mixed with 0.5 wt% of sodium myristoyl-N-methyl- ⁇ -alanine (pulverized to 100 ⁇ m or less) for 3 minutes in a cross-rotary mixer produced by Meiwa Kogyo Co., Ltd. and tableted at a compression pressure shown in Tables 4 and 5 to obtain 1,000 tablets, using a tableting machine, Clean Press Collect 18K produced by Kikusui Seisakusho Co., Ltd. which was modified. Thus, samples (4-1) through (4-44) were obtained. The tablets weighed about 11g and were in a cylindrical form having a diameter of 30mm.
  • the accommodating container 33 includes: a container main body 331 for accommodating a plural of processing tablets, the configuration of which is like a hollow square hole; outlet member 332 having an opening for discharging the tablets connecting accommodating container main body 33, a cap member 333 for closing the other opening of the container main body 331; and a sliding cover member 334 capable of being slid on a rail of the opening 332.
  • Three sets of partition walls 331S are integrally fixed inside the container 331, so that the inside of the container 331 is divided into four chambers 331A, 331B, 331C, 331D.
  • the approximately cylindrical tablets of solid processing agent J are longitudinally accommodated under the condition that each outer circumference externally contacts each other.
  • 10 tablets of solid processing agent J1A to J10A are accommodated in the first chamber 331A
  • 10 tablets of solid processing agent J1B are accommodated in the second chamber 331B.
  • the tablets J1C and J1D are respectively accommodated in the chambers.
  • a projection 331E is projected from the bottom surface of each chamber of the container main body 331.
  • This projection 331E comes into a point of the outer circumferential surface of the tablet of solid processing agent J, so that the tablet can be easily moved, and powder separated from the tablet of solid processing agent J drops from the top of the projection 331E. Separated powder accumulates in a groove formed under the projection 331E. Accordingly, even when the powder is deposited in the groove, no problems are caused because the tablet of solid processing agent J moves on the projection 331E.
  • a rail is provided on the both side of the outlet of the opening 332 and slide cover member 334 having a groove can slide on the rail by the groove.
  • Protrusions on the both edges under slide cover member 334 connect means described later capable of opening and closing the opening 332 by moving slide cover member 334.
  • pin 332B engaged with cam of loading means for a container described below.
  • the rear surface 333A of cap means 333 is pressed by press means of the loading means and container 33 is press-contacts the normal position of supplying means. Further, rear surface 333A is integrated with discriminating protrusion 333B and prevents erroneously loading on the wrong container.
  • CD-3 4-Amino-3-methyl-N-ethyl-N-( ⁇ -methanesulfonamidoethyl)aniline ⁇ 2/3H2SO4 ⁇ H2O (hereinafter referred to as CD-3) 15,000g
  • Procedure (5-2) was carried out, except that 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)aniline ⁇ sulfate (hereinafter referred to as CD-4) was used instead of CD-3. Thus, sample (5-3) was obtained.
  • CD-4 4-Amino-3-methyl-N-ethyl-N-( ⁇ -hydroxyethyl)aniline ⁇ sulfate
  • CD-4 10,000g Bis(sodiumsulfoethyl)hydroxylamine 3,000g D-mannitol 1,500g
  • the above compounds was independently pulverized in the same manner as in Procedure (1-2).
  • the resulting powders were mixed for 3 minutes in a stirring granulator, and granulated for about 7 minutes while 900ml of a 10 wt% bis(sodiumsulfoethyl)hydroxylamine solution water was added at a rate of 750ml/min.
  • the resulting granules were dried in the same manner as in Procedure (5-2). Dressing was carried out according to drying methods and screens shown in Table 7. Thereafter, the resulting sample was dried to have a moisture content of 2 wt% or less. Thus, samples (5-24) through (5-33) were obtained.
  • Procedure (5-6) was carried out, except that CD-3 was used instead of CD-4. Thus, samples (5-34) through (5-43) were obtained.
  • Example 1 The above samples were evaluated for fine powder occurrence and the fluctuation in the same manner as in Example 1. The results are shown in Tables 6 and 7. The evaluation criteria were the same as Example 1.
  • the above compounds was independently pulverized in the same manner as in Procedure (1-2).
  • the resulting powders were mixed for 3 minutes in a stirring granulator, and granulated for about 7 minutes while a 10 wt% bis(sodiumsulfoethyl)hydroxylamine solution was added in an amount (in terms of water) shown in Table 8 at a rate of 750ml/min.
  • the resulting granules were dried in the same manner as in Procedure (5-2). Dressing was carried out during and after drying using a 1.5 mm screen. Thus, samples (6-1) through (6-14) were obtained.
  • Example 5 The resulting samples were evaluated for coloration and processability after storage in the same manner as in Example 5. The evaluation criteria were the same as Example 5.
  • the resulting samples were evaluated for the p-phenylene diamine compound content before and after the manufacture.
  • the content was evaluated according to the following criteria, the content before the manufacture being represented as 100%.
  • Samples prepared in Examples 5 and 6 (shown in Tables 9, 10 and 11) were mixed with 1.0 wt% of sodium myristoyl-N-methyl- ⁇ -alanine (pulverized to 100 ⁇ m or less) for 3 minutes in a cross-rotary mixer produced by Meiwa Kogyo Co., Ltd. and tableted at a compression pressure shown in Tables 9, 10 and 11, using a tableting machine, Clean Press Collect 18K produced by Kikusui Seisakusho Co., Ltd. which was modified. The tablets weighed about 9g and were in a cylindrical form having a diameter of 30mm. Thus, samples (7-1) through (7-57) were obtained.
  • Example 4 The samples were evaluated for fine powder occurrence, fluctuation and hardness in the same manner as in Example 4. The evaluation criteria were the same as Example 4.
  • the above compound was pulverized and granulated in the same method as in Procedure (1-2). Granulation was carried out for about 5 minutes while 600ml of water was sprayed at a rate of 750ml/min. The resulting granules were dried in a fluid bed drier to have a moisture content of 2 wt% or less, while the temperature of drying air was controlled to be 50 to 65°C. The resulting granules were dressed according to methods shown in Table 12 using screens shown in Table 12 and dried to have a moisture content of 2 wt% or less. Thus, samples (8-2) through (8-12) were obtained.
  • Procedure (5-2) was carried out, except that bis(sodiumsulfoethyl)hydroxylamine was used instead of hydroxylamine sulfate. Thus, samples (8-13) through (8-23) were obtained.
  • the above compounds was independently pulverized at 30°C and 50%RH in the same manner as in Procedure (1-2).
  • the resulting powders were mixed for 3 minutes in a stirring granulator and granulated for about 5 minutes while 500ml of water was sprayed at a rate of 750ml/min.
  • the resulting granules were dried in a fluid bed drier, while the temperature of drying air was controlled to be 50 to 65°C.
  • the resulting granules were dressed according to methods shown in Table 13 using screens shown in Table 13 and dried to have a moisture content of 2 wt% or less. Thus, samples (8-24) through (8-33) were obtained.
  • Example 1 The above samples were evaluated for fine powder occurrence and the fluctuation in the same manner as in Example 1. The results are shown in Tables 12 and 13. The evaluation criteria were the same as Example 1.
  • the content was evaluated according to the following criteria, the content before the manufacture being represented as 100%.
  • Procedures (8-4) and (8-5) were carried out, except that water was added in an amount (based on the total content of the compounds) shown in Table 14.
  • the dressing was carried out during and after drying using a 1.5 mm mesh screen. Thus, samples (9-1) through (9-12) were obtained.
  • the content was evaluated according to the following criteria, the content before the manufacture being represented as 100%.
  • Samples prepared in Examples 8 and 9 (shown in Tables 15, 16 and 17) were mixed with 0.5 wt% of sodium myristoyl-N-methyl- ⁇ -alanine (pulverized to 100 ⁇ m or less) for 3 minutes in a cross-rotary mixer, and then, tableted at a compression pressure shown in Tables 15, 16 and 17 in the same manner as in Procedure (7-1).
  • the resulting tablets weighed about 11g and were in a cylindrical form having a diameter of 30mm.
  • Example 7 The samples were evaluated for fine powder occurrence, fluctuation, slidability and hardness in the same manner as in Example 7. The results are shown in Tables 15, 16 and 17. The evaluation criteria were the same as Example 7.
  • the above compounds was pulverized, mixed, and granulated in the same manner as in Procedure (8-2).
  • the resulting powders were granulated for about 5 minutes while 450ml of water was sprayed at a rate of 750ml/min.
  • the resulting granules were dried in a fluid bed drier, while the temperature of drying air was controlled to be 50 to 65°C, and dressed according to methods shown in Table 18 using screens shown in Table 18.
  • the resulting granules were dried to have a moisture content of 2 wt% or less. Thus, samples (11-2) through (11-12) were obtained.
  • Procedure (11-2) was carried out, except that ammonium ferric 1,3-propanediaminetetraacetate ⁇ monohydrate (hereinafter referred to as PDTA-Fe ⁇ NH4 ⁇ H2O) or ammonium ferric diethylenetriaminepentaacetate ⁇ monohydrate (hereinafter referred to as DTPA-Fe ⁇ NH4H ⁇ H2O) was used instead of EDTA-Fe ⁇ Na ⁇ 3H2O.
  • samples (11-13) through (11-27) were obtained.
  • Example 1 The above samples were evaluated for fine powder occurrence and the fluctuation in the same manner as in Example 1. The results are shown in Tables 18 and 19. The evaluation criteria were the same as Example 1.
  • Procedure (12-1) was carried out, except that EDTA-Fe ⁇ NH4 ⁇ 2H2O or DTPA-Fe ⁇ NH4H ⁇ H2O was used instead of PDTA-Fe ⁇ NH4 ⁇ H2O. Thus, samples (12-12) through (12-26) were obtained.
  • Example 11 The evaluation was carried out in the same manner as in Example 11. The evaluation criteria was the same as Example 11.
  • Samples prepared in Examples 11 and 12 (shown in Tables 22, 23 and 24) were mixed with 1.0 wt% of sodium N-lauroylsarcosine (pulverized to 100 ⁇ m or less) for 3 minutes in a cross-rotary mixer, and then, tableted at a compression pressure shown in Tables 22, 23 and 24 in the same manner as in Procedure (7-1).
  • the resulting tablets weighed about 11g and were in a cylindrical form having a diameter of 30mm. Thus, samples (7-1) through (7-57) were obtained.
  • Example 10 The samples were evaluated in the same manner as in Example 10. The evaluation criteria were the same as Example 10.
  • the above compounds was pulverized, mixed, and granulated in the same manner as in Procedure (8-2).
  • the resulting powders were granulated for about 3 minutes while 450ml of water was sprayed at a rate of 750ml/min.
  • the resulting granules were dried in a fluid bed drier, while the temperature of drying air was controlled to be 50 to 60°C, and dressed according to methods shown in Table 25 using screens shown in Table 25.
  • the resulting granules were dried to have a moisture content of 2 wt% or less. Thus, samples (14-2) through (14-12) were obtained.
  • Ammonium thiosulfate 14,000g Sodium sulfite 1,000g Disodium ethylenediaminetetraacetate 100g Potassium carbonate 100g Pineflow 300g
  • Example 1 The above samples were evaluated for fine powder occurrence due to vibration, the fluctuation and blocking property due to moisture absorption in the same manner as in Experiments (1-1) through (1-3) of Example 1. The results are shown in Tables 25 and 26. The evaluation criteria were the same as Example 1.
  • the compounds were independently pulverized, mixed and granulated in the same manner as in Procedure (14-3), except that water was added in an amount shown in Table 27 (based on the total weight of the compounds).
  • the resulting granules were dressed during and after drying using a 1.5mm screen. Thus, samples (15-1) through (15-7) were obtained.
  • the compounds were independently pulverized, mixed and granulated in the same manner as in Procedure (14-4), except that water was added in an amount shown in Table 27 (based on the total weight of the compounds).
  • the resulting granules were dressed during and after drying using a 1.5mm screen. Thus, samples (15-8) through (15-14) were obtained.
  • Samples (15-1) through (15-14) were evaluated for the content of thiosulfate before and after the manufacture.
  • the content was evaluated according to the following criteria, the content before the manufacture being represented as 100%.
  • Samples prepared in Examples 14 and 15 (shown in Tables 28, 29 and 30) were mixed with 0.5 wt% of sodium N-lauroylsarcosine (pulverized to 100 ⁇ m or less) for 3 minutes in a cross-rotary mixer, and then, tableted at a compression pressure shown in Tables 28, 29 and 30 in the same manner as in Procedure (7-1).
  • the resulting tablets weighed about 11g and were in a cylindrical form having a diameter of 30mm.
  • Example 4 The samples were evaluated for fine powder occurrence after storage, fluctuation, blocking property due to moisture absorption after storage and hardness in the same manner as in Example 4. The evaluation criteria were the same as Example 4.
  • o-Phenylphenol 200g Ethylenediaminetetraacetic acid 2,000g Disodium ethylenediaminetetraacetate 2,500g Polyethylene glycol#4000 (produced by Nihon Yushi Co., Ltd.) 1,500g Tetrasodium 1-hydroxyethylidene-1,1-diphosphonate 9,000g
  • o-Phenylphenol 200g Ethylenediaminetetraacetic acid 2,000g Disodium ethylenediaminetetraacetate 2,500g Polyethylene glycol#4000 (produced by Nihon Yushi Co., Ltd.) 1,500g Tetrasodium 1-hydroxyethylidene-1,1-diphosphonate 9,000g
  • the above compounds were pulverized, mixed, and granulated in the same manner as in Procedure (8-2).
  • the powders were granulated for 3 minutes while water was sprayed in an amount shown in Table 31 (based on the total weight of the compounds) at a rate of 750ml/min.
  • the resulting granules were dried in a fluid bed drier, while the temperature of drying air was controlled to be 50 to 65°C, and dressed according to methods shown in Table 31 using screens shown in Table 31.
  • the resulting granules were dried to have a moisture content of 2 wt% or less. Thus, samples (17-2) through (17-17) were obtained.
  • Example 1 The above samples were evaluated for fine powder occurrence due to vibration after storage, the fluctuation and blocking property due to moisture absorption after storage in the same manner as in Example 1. The evaluation criteria were the same as Example 1.
  • Example 17 Samples prepared in Example 17 (shown in Tables 33 and 34) were mixed with 0.5 wt% of sodium N-lauroylsarcosine (pulverized to 100 ⁇ m or less) for 3 minutes in a cross-rotary mixer, and then, tableted at a compression pressure shown in Tables 33 and 34 in the same manner as in Procedure (7-1). The resulting tablets weighed about 10.5g and were in a cylindrical form having a diameter of 30mm.
  • Example 4 The samples were evaluated in the same manner as in Example 4. The evaluation criteria were the same as Example 4.
  • the above compounds were pulverized, mixed, and granulated in the same manner as in Procedure (8-2).
  • the powders were granulated for 3 minutes while water was sprayed in an amount shown in Table 35 (based on the total weight of the compounds) at a rate of 750ml/min.
  • the resulting granules were dried in a fluid bed drier, while the temperature of drying air was controlled to be 40 to 60°C, and dressed according to methods shown in Table 35 using screens shown in Table 35.
  • the resulting granules were dried to have a moisture content of 2 wt% or less. Thus, samples (19-2) through (19-18) were obtained.
  • Example 1 The above samples were evaluated for fine powder occurrence due to vibration after storage and the fluctuation in the same manner as in Example 1. The evaluation criteria were the same as Example 1. The results are shown in Tables 35 and 36.
  • Example 19 Samples prepared in Example 19 (shown in Tables 37 and 38) were tableted at a compression pressure shown in Tables 37 and 38 in the same manner as in Procedure (7-1). The resulting tablets weighed about 8.5g and were in a cylindrical form having a diameter of 30mm.
  • Example 4 The samples were evaluated for fine powder occuerrence due to vibration after storage, fluctuation and hardness in the same manner as in Example 4. The evaluation criteria were the same as Example 4.
  • Example 5 The samples were evaluated for fluctuation and coloration after storage in the same manner as in Example 5. The evaluation criteria were the same as Example 5.
  • Example 4 The samples were evaluated for fluctuation and expansion due to moisture absorption in the same manner as in Example 4. The evaluation criteria were the same as Example 4. The results are shown in Table 40.
  • Tableting property was evaluated during continuously tableting.
  • the evaluation criteria were as follows:
  • Example 5 The samples were evaluated for fluctuation and coloration after storage in the same manner as in Example 11. The results are shown in Table 41. The evaluation criteria were the same as Example 5.
  • the granular sample containing a ferric complex of an amino polycarboxylic acid of Examples 11 and the granular sample containing a thiosulfate of Examples 14 were mixed in an amount shown in Table 42, using samples shown in Table 42 and further mixed with 5 wt% of polyethylene glycol#4000 (produced by Nihon Yushi Co., Ltd.) for 10 minutes in a cross-rotary mixer. To the resulting mixture were added 0.5 wt% of sodium N-lauroylsarcosine (pulverized to 100 ⁇ m or less) and mixed for further 3 minutes. The resulting granules were tableted at a compression pressure of 1400 kg/cm2 in the same manner as in Example 13 to obtain 1,000 tablets. Thus, samples (24-1) through (24-6) were obtained.
  • Example 13 The samples were evaluated for fluctuation and slidability in the same manner as in Example 13. The results are shown in Table 42. The evaluation criteria were the same as Example 13.

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EP95302458A 1994-04-19 1995-04-12 Méthode de fabrication de composition solide pour le traitement de matériaux photographiques à l'halogénure d'argent sensibles à la lumière Expired - Lifetime EP0678782B1 (fr)

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EP0682289A2 (fr) * 1994-05-09 1995-11-15 Konica Corporation Produits chimiques sous la forme de granulés pour le développement photographique en couleur
EP0711592A3 (fr) * 1994-11-11 1997-03-05 Konishiroku Photo Ind Procédé de fabrication d'une composition solide pour le traitement des matériaux photographiques à l'halogénure d'argent sensibles à la lumière
EP0888812A1 (fr) * 1997-07-01 1999-01-07 Konica Corporation Composition solide de traitement pour matériau photographique à l'halogénure d'argent sensible à la lumière et procédé de fabrication pour ladite
EP0964303A1 (fr) * 1998-06-12 1999-12-15 Konica Corporation Méthode pour la préparation d'un agent granuleux et méthode pour la préparation d'un comprimé
EP1003077A2 (fr) * 1998-11-18 2000-05-24 Tetenal Photowerk GmbH & Co Procédé de fabrication de produits chimiques photographiques sous forme de comprimé

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EP0679940A1 (fr) 1994-04-28 1995-11-02 Konica Corporation Composition solide de traitement pour matériaux photographiques à l'halogénure d'argent sensibles à la lumière
EP0679940B1 (fr) * 1994-04-28 2001-01-24 Konica Corporation Composition solide de traitement pour matériaux photographiques à l'halogénure d'argent sensibles à la lumière
EP0682289A2 (fr) * 1994-05-09 1995-11-15 Konica Corporation Produits chimiques sous la forme de granulés pour le développement photographique en couleur
EP0682289A3 (fr) * 1994-05-09 1996-03-13 Konishiroku Photo Ind Produits chimiques sous la forme de granulés pour le développement photographique en couleur.
US5607822A (en) * 1994-05-09 1997-03-04 Konica Corporation Photographic color-developing chemicals in the form of granules
EP0711592A3 (fr) * 1994-11-11 1997-03-05 Konishiroku Photo Ind Procédé de fabrication d'une composition solide pour le traitement des matériaux photographiques à l'halogénure d'argent sensibles à la lumière
EP0888812A1 (fr) * 1997-07-01 1999-01-07 Konica Corporation Composition solide de traitement pour matériau photographique à l'halogénure d'argent sensible à la lumière et procédé de fabrication pour ladite
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EP0964303A1 (fr) * 1998-06-12 1999-12-15 Konica Corporation Méthode pour la préparation d'un agent granuleux et méthode pour la préparation d'un comprimé
EP1003077A2 (fr) * 1998-11-18 2000-05-24 Tetenal Photowerk GmbH & Co Procédé de fabrication de produits chimiques photographiques sous forme de comprimé
EP1003077A3 (fr) * 1998-11-18 2000-09-20 Tetenal Photowerk GmbH & Co Procédé de fabrication de produits chimiques photographiques sous forme de comprimé

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DE69520079T2 (de) 2001-06-21
US5635342A (en) 1997-06-03
EP0678782B1 (fr) 2001-02-14

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